EP0047206B1 - Process for preparation of aminoalcohols polyoxa-alkylated or polyoxa-arylated and their use as cation complexing agents - Google Patents
Process for preparation of aminoalcohols polyoxa-alkylated or polyoxa-arylated and their use as cation complexing agents Download PDFInfo
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- EP0047206B1 EP0047206B1 EP81401325A EP81401325A EP0047206B1 EP 0047206 B1 EP0047206 B1 EP 0047206B1 EP 81401325 A EP81401325 A EP 81401325A EP 81401325 A EP81401325 A EP 81401325A EP 0047206 B1 EP0047206 B1 EP 0047206B1
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- European Patent Office
- Prior art keywords
- amine
- bis
- equal
- aza
- formula
- Prior art date
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- 150000001414 amino alcohols Chemical class 0.000 title claims abstract description 22
- 150000001768 cations Chemical class 0.000 title claims abstract description 7
- 238000000034 method Methods 0.000 title claims description 22
- 238000002360 preparation method Methods 0.000 title claims description 11
- 239000008139 complexing agent Substances 0.000 title claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 14
- -1 alkyl radical Chemical class 0.000 claims description 13
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 3
- YUDRVAHLXDBKSR-UHFFFAOYSA-N [CH]1CCCCC1 Chemical compound [CH]1CCCCC1 YUDRVAHLXDBKSR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 2
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 claims description 2
- 238000005984 hydrogenation reaction Methods 0.000 claims 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 claims 1
- 230000007928 solubilization Effects 0.000 abstract description 12
- 238000005063 solubilization Methods 0.000 abstract description 12
- 238000010668 complexation reaction Methods 0.000 abstract description 2
- FNAZRRHPUDJQCJ-UHFFFAOYSA-N henicosane Chemical compound CCCCCCCCCCCCCCCCCCCCC FNAZRRHPUDJQCJ-UHFFFAOYSA-N 0.000 description 40
- YCOZIPAWZNQLMR-UHFFFAOYSA-N pentadecane Chemical compound CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 40
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 28
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 26
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 24
- NDJKXXJCMXVBJW-UHFFFAOYSA-N heptadecane Chemical compound CCCCCCCCCCCCCCCCC NDJKXXJCMXVBJW-UHFFFAOYSA-N 0.000 description 20
- VTXJIDBQMAXDIY-QKBMRJQYSA-N C[C@H]1CN[C@]2(C[C@H]3O[C@]4(CC(=C)[C@H]5O[C@@](O)([C@H](O)[C@@H]6C[C@H]7O[C@@]8(CC[C@]9(CC=C[C@H](O9)\C=C\CCC(O)=O)O8)[C@H](C)C[C@H]7O6)[C@H](C)[C@H](O)[C@@H]5C)C[C@@H](C)C[C@@H](O4)[C@H]3O2)[C@@H](C)C1 Chemical compound C[C@H]1CN[C@]2(C[C@H]3O[C@]4(CC(=C)[C@H]5O[C@@](O)([C@H](O)[C@@H]6C[C@H]7O[C@@]8(CC[C@]9(CC=C[C@H](O9)\C=C\CCC(O)=O)O8)[C@H](C)C[C@H]7O6)[C@H](C)[C@H](O)[C@@H]5C)C[C@@H](C)C[C@@H](O4)[C@H]3O2)[C@@H](C)C1 VTXJIDBQMAXDIY-QKBMRJQYSA-N 0.000 description 18
- 150000001412 amines Chemical class 0.000 description 18
- BJQWYEJQWHSSCJ-UHFFFAOYSA-N heptacosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCC BJQWYEJQWHSSCJ-UHFFFAOYSA-N 0.000 description 16
- LQERIDTXQFOHKA-UHFFFAOYSA-N nonadecane Chemical compound CCCCCCCCCCCCCCCCCCC LQERIDTXQFOHKA-UHFFFAOYSA-N 0.000 description 16
- YKNWIILGEFFOPE-UHFFFAOYSA-N pentacosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCC YKNWIILGEFFOPE-UHFFFAOYSA-N 0.000 description 16
- FIGVVZUWCLSUEI-UHFFFAOYSA-N tricosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCC FIGVVZUWCLSUEI-UHFFFAOYSA-N 0.000 description 14
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- ZCYXXKJEDCHMGH-UHFFFAOYSA-N nonane Chemical compound CCCC[CH]CCCC ZCYXXKJEDCHMGH-UHFFFAOYSA-N 0.000 description 8
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 8
- 150000003254 radicals Chemical class 0.000 description 8
- 125000004429 atom Chemical group 0.000 description 7
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 6
- JXTPJDDICSTXJX-UHFFFAOYSA-N n-Triacontane Natural products CCCCCCCCCCCCCCCCCCCCCCCCCCCCCC JXTPJDDICSTXJX-UHFFFAOYSA-N 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 230000000536 complexating effect Effects 0.000 description 4
- 150000003335 secondary amines Chemical class 0.000 description 4
- 150000003567 thiocyanates Chemical class 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000007868 Raney catalyst Substances 0.000 description 2
- 229910000564 Raney nickel Inorganic materials 0.000 description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 description 2
- IULVQKKXKTUYME-UHFFFAOYSA-N 1-hydroperoxynonane Chemical compound CCCCCCCCCOO IULVQKKXKTUYME-UHFFFAOYSA-N 0.000 description 1
- CFZDXEQGLDHSNV-UHFFFAOYSA-N 1-hydroperoxyperoxyperoxyheptadecane Chemical compound CCCCCCCCCCCCCCCCCOOOOOO CFZDXEQGLDHSNV-UHFFFAOYSA-N 0.000 description 1
- FJNCXZZQNBKEJT-UHFFFAOYSA-N 8beta-hydroxymarrubiin Natural products O1C(=O)C2(C)CCCC3(C)C2C1CC(C)(O)C3(O)CCC=1C=COC=1 FJNCXZZQNBKEJT-UHFFFAOYSA-N 0.000 description 1
- 0 CCC(CC)N* Chemical compound CCC(CC)N* 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000005915 ammonolysis reaction Methods 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000004969 haloethyl group Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
Definitions
- the present invention relates to a process for the preparation of polyoxaalkylated or polyoxaarylated amino alcohols which can be used as cation complexing agents.
- Polyoxaalkylated amino alcohols have already been described. These include (English Patent No. 897,163) those having the formula:
- nickel catalysts of the Raney or Harshaw nickel type; the amount of catalyst may be between 1 and 15% of the weight of bis (polyoxaalkyl) amine or bis (polyoxaaryl) amine and preferably between 2 and 6%.
- the polyalkylene glycol molar ratio of formula (II) / bis (polyoxaalkyl) amine or bis (polyoxaaryl) amine of formula (III) may also be between 1, 5 and 10 times the stoichiometry and preferably between 2 and 6 times the stoichiometry .
- the process which is the subject of the invention may preferably be carried out in the presence of hydrogen, at a pressure below 20 bars, and generally at autogenous pressure, with vigorous stirring until the polyalkylene glycol disappears; this operation lasts from 2 to 10 hours and general 3 to 4 hours.
- the amount of hydrogen that can be used is of the order of 1 to 10% of the weight of alkylene glycol used and preferably of the order of 1 to 5%.
- the water formed during the reaction can be removed from the reaction medium using a gas stream, such as hydrogen when the latter has been used or nitrogen.
- the polyoxaalkylated or polyoxaarylated amino alcohols obtained according to the process of the invention can be used as cation complexing agents.
- the present invention also relates to this application.
- the yield reaches 55% on the secondary amine used.
- the yield on the charged secondary amine reaches 71%.
- the yield relative to the secondary amine used is 71.5%.
- the yield relative to the secondary amine is 72%.
- the test is also carried out in the absence of complexing agent to be tested.
- Example 6 The test described in Example 6 is carried out using as a complexing agent to test the product of Example 4.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Description
La présente invention vise un procédé de préparation d'aminoalcools polyoxaalkylés ou polyoxaarylés pouvant être utilisés comme agents de complexation de cations.The present invention relates to a process for the preparation of polyoxaalkylated or polyoxaarylated amino alcohols which can be used as cation complexing agents.
Des aminoalcools polyoxaalkylés ont déjà été décrits. Il s'agit notamment (brevet anglais no 897 163) de ceux ayant pour formule:
Ils peuvent être préparés par action d'une alca- nolamine HO-alkylène-NH2 sur par exemple un chlorure d'alkoxypolyéthylèneoxyéthyl:
Il est connu d'après le brevet français no 2402473 de préparer des di(hydroxypolyoxaal- kyl)mono(alkylétherpolyoxaaryl)amine par oxy- éthylation d'une amine à fonction éther obtenue par propoxylation d'un alcool suivie d'une ammo- nolyse.It is known from French patent no. 2402473 to prepare di (hydroxypolyoxaalkyl) mono (alkyl etherpolyoxaaryl) amine by oxyethylation of an amine with an ether function obtained by propoxylation of an alcohol followed by ammonolysis .
Il a également été proposé dans le brevet européen no 5094 de préparer des tris(polyoxaal- kyl)amines par action d'un sel de métal alcalin d'un monoalcoyléther d'une éthylène glycol et d'une tris(halogénoéthyl)amine.It has also been proposed in European Patent No. 5094 to prepare tris (polyoxalkyl) amines by the action of an alkali metal salt of a monoalkyl ether of an ethylene glycol and a tris (haloethyl) amine.
Aucun des documents ci-dessus cités ne donne un enseignement quant à la préparation sélective d'aminoalcools présentant un atome d'azote trisubstitué par deux chaînes polyoxaalkylés ou arylés et une chaine polyoxahydroxylée présentant un nombre bien défini de motifs oxyalky- lènes.None of the documents cited above teaches as to the selective preparation of amino alcohols having a nitrogen atom trisubstituted by two polyoxaalkylated or arylated chains and a polyoxahydroxylated chain having a well defined number of oxyalkylene units.
Selon l'invention le procédé de préparation d'aminoalcools polyoxaalkylés ou polyoxaarylés de formule:
- - R1, R2, R3 et R4 sont semblables ou différents et représentent:
- · un atome d'hydrogène
- · un radical alkyle contenant de 1 à 4 atomes de carbone
- - R5représente:
- ·un radical alkyle contenant de 1 à 12 atomes de carbone, éventuellement substitué par un groupe phényle
- ·un radical cycloalkyle contenant de 3 à 12 atomes de carbone
- ·un radical phényle éventuellement substitué par un groupe alkyle contenant de 1 à 12 atomes de carbone
- - n est un nombre entier supérieur ou égal à 1 et inférieur ou égal à 9
- - m est un nombre entier supérieur ou égal à 1 et inférieur ou égal à 10 est caractérisé en ce que l'on fait réagir un polyalkylène glycol de formule:
- - R 1 , R 2 , R 3 and R 4 are similar or different and represent:
- · A hydrogen atom
- · An alkyl radical containing from 1 to 4 carbon atoms
- - R 5 represents:
- · An alkyl radical containing from 1 to 12 carbon atoms, optionally substituted by a phenyl group
- · A cycloalkyl radical containing from 3 to 12 carbon atoms
- · A phenyl radical optionally substituted by an alkyl group containing from 1 to 12 carbon atoms
- - n is an integer greater than or equal to 1 and less than or equal to 9
- - m is an integer greater than or equal to 1 and less than or equal to 10 is characterized in that a polyalkylene glycol of formula is reacted:
La présente invention vise à titre préférentiel un procédé de préparation d'aminoalcools polyoxaalkylés ou polyoxaarylés de formule (I) dans lesquels:
- - Ri, R2, R3, R4 sont semblables ou différents et représentent:
- · un atome d'hydrogène
- ·un radical méthyle
- - R5représente:
- · un radical alkyle contenant de 1 à 6 atomes de carbone,
et tout particulièrement de 1 à 4 atomes de carbone,
éventuellement substitué par un groupe phényle; - ·un radical cyclohexyle
- ·un radical phényle éventuellement substitué par un groupe alkyle contenant de 1 à 4 atomes de carbone
- · un radical alkyle contenant de 1 à 6 atomes de carbone,
- - n représente un nombre entier supérieur ou égal à 1 et inférieur ou égal à 5, et tout particulièrement égal à 1, 2 ou 3
- - m représente un nombre entier supérieur ou égal à 1 et inférieur ou égal à 6, et tout particulièrement égal à 1,2,3 ou 4.
- - R i , R 2 , R 3 , R 4 are similar or different and represent:
- · A hydrogen atom
- · A methyl radical
- - R 5 represents:
- · An alkyl radical containing from 1 to 6 carbon atoms,
and very particularly from 1 to 4 carbon atoms,
optionally substituted with a phenyl group; - · A cyclohexyl radical
- · A phenyl radical optionally substituted by an alkyl group containing from 1 to 4 carbon atoms
- · An alkyl radical containing from 1 to 6 carbon atoms,
- - n represents an integer greater than or equal to 1 and less than or equal to 5, and very particularly equal to 1, 2 or 3
- - m represents an integer greater than or equal to 1 and less than or equal to 6, and very particularly equal to 1,2,3 or 4.
A titre d'exemples d'aminoalcools polyoxaalkylés pouvant être préparés selon le procédé de la présente invention, on peut citer:
- - le N(hydroxy-5'oxa-3'pentyl)aza-5 dioxa-2,8 nonane
- - le N(hydroxy-5'oxa-3'pentyl)aza-6 dioxa-3,9 undecane
- - le N(hydroxy-5'oxa-3'pentyl)aza-7 diox-4,10 tridécane
- - le N(hydroxy-5'oxa-3'pentyl)aza-8 dioxa-5,11 pentadecane
- - le N(hydroxy-5'oxa-3'pentyl)aza-8 tetraoxa-2,5,11,14 pentadecane
- - le N(hydroxy-5'oxa-3'pentyl)aza-9 tetraoxa-3,6,12,15 heptadecane
- - le N(hydroxy-5'oxa-3'pentyl)aza-10 tetraoxa-4,7,13,16 nonadecane
- - le N(hydroxy-5'oxa-3'pentyl)aza-11 tetraoxa-5,8,14,17 heneicosane
- - le N(hydroxy-5'oxa-3'pentyl)aza-11 hexaoxa-2,5,8,14,17,20 heneicosane
- - le N(hydroxy-5'oxa-3'pentyl)aza-12 hexaoxa-3,6,9,15,18,21 tricosane
- - le N(hydroxy-5'oxa-3'pentyl)aza-13 hexaoxa-4,7,10,16,19,22 pentacosane
- - le N(hydroxy-5'oxa-3'pentyl)aza-14 hexaoxa-5,8,11,17,20,23 heptacosane
ayant pour formule: - - le N(hydroxy-8'dioxa-3,6'octyl)aza-5 dioxa-2,8 nonane
- - le N(hydroxy-8'dioxa-3,6'octyl)aza-6 dioxa-3,9 undecane
- - le N(hydroxy-8'dioxa-3,6'octyl)aza-7 dioxa-4,10tridecane
- - le N(hydroxy-8'dioxa-3,6'octyl)aza-8 dioxa-5,11 pentadecane
- - le N(hydroxy-8'dioxa-3,6'octyl)aza-8 tetraoxa-2,5,11,14 pentadecane
- - le N(hydroxy-8'dioxa-3,6'octyl)aza-9 tetraoxa-3,6,12,15 heptadecane
- - le N(hydroxy-8'dioxa-3,6'octyl)aza-10 tetraoxa-4,7,13,16 nonadecane
- - le N(hydroxy-8'dioxa-3,6'octyl)aza-11 tetraoxa-5,8,14,17 heneicosane
- - le N(hydroxy-8'dioxa-3,6'octyl)aza-11 hexaoxa-2,5,8,14,17,20 heneicosane
- - le N(hydroxy-8'dioxa-3,6'octyl)aza-12 hexaoxa-3,6,9,15,18,21 tricosane
- - le N(hydroxy-8'dioxa-3,6'octyl)aza-13 hexaoxa-4,7,10,16,19,22 pentacosane
- - le N(hydroxy-8'dioxa-3,6'octyl)aza-14 hexaoxa-5,8,11,17,20,23 heptacosane
ayant pourformule: - - le N(hydroxy-11'trioxa-3',6',9'undecyl)aza-5 dioxa-2,8 nonane
- - le N(hydroxy-11'trioxa-3',6',9'undecyl)aza-6 dioxa-3,9 undecane
- - le N(hydroxy-11'trioxa-3',6',9'undecyl)aza-7 dioxa-4,10tridecane
- - le N(hydroxy-11'trïoxa-3',6',9'undecyl)aza-8 dioxa-5,11 pentadecane
- - le N(hydroxy-11'trioxa-3',6',9'undecyl)aza-8 tetraoxa-2,5,11,14 pentadecane
- - le N(hydroxy-11'trioxa-3',6',9'undecyl)aza-9 tetraoxa-3,6,12,15 heptadecane
- - le N(hydroxy-11'trioxa-3',6',9'undecyl)aza-10 tetraoxa-4,7,13,16 nonadecane
- - le N(hydroxy-11'trioxa-3',6',9'undecyl)aza-11 tetraoxa-5,8,14,17 heneicosane
- - le N(hydroxy-11'trioxa-3',6',9'undecyl)aza-11 hexaoxa-2,5,8,14,17,20 heneicosane
- - le N(hydroxy-11'trioxa-3',6',9'undecyl)aza-12 hexaoxa-3,6,9,15,18,21 tricosane
- - le N(hydroxy-11'trioxa-3',6',9'undecyl)aza-13 hexaoxa-4,7,10,16,19,22 pentacosane
- - le N(hydroxy-11'trioxa-3',6',9'undecyl)aza-14 hexaoxa-5,8,11,17,20,23 heptacosane
ayant pour formule:
ainsi que les aminoalcools polyoxaarylés ayant pour formule:
- - N (hydroxy-5'oxa-3'-pentyl) aza-5-dioxa-2,8 nonane
- - N (hydroxy-5'-oxa-3'pentyl) aza-6-3,9 dioxa undecane
- - N (hydroxy-5'oxa-3'pentyl) aza-7 diox-4,10 tridecane
- - N (hydroxy-5'-oxa-3 'pentyl) aza-dioxa-8 5.11 pentadecane
- - N (hydroxy-5'oxa-3'pentyl) aza-8 tetraoxa-2,5,11,14 pentadecane
- - N (hydroxy-5'oxa-3'pentyl) aza-9 tetraoxa-3,6,12,15 heptadecane
- - N (hydroxy-5'oxa-3'pentyl) aza-10 tetraoxa-4,7,13,16 nonadecane
- - N (hydroxy-5'-oxa-3 'pentyl) aza-5,8,14,17-tetraoxa 11 heneicosane
- - N (hydroxy-5'oxa-3'pentyl) aza-11 hexaoxa-2,5,8,14,17,20 heneicosane
- - N (hydroxy-5'oxa-3'pentyl) aza-12 hexaoxa-3,6,9,15,18,21 tricosan
- - N (hydroxy-5'oxa-3'pentyl) aza-13 hexaoxa-4,7,10,16,19,22 pentacosane
- - N (hydroxy-5'oxa-3'pentyl) aza-14 hexaoxa-5,8,11,17,20,23 heptacosane
having the formula: - - N (hydroxy-8 'dioxa-3,6'octyl) aza-5-dioxa-2,8 nonane
- - N (hydroxy-8'dioxa-3,6'octyl) aza-6 dioxa-3,9 undecane
- - N (hydroxy-8'dioxa-3,6 ' octyl) aza-7 dioxa-4,10tridecane
- - N (hydroxy-8'dioxa-3,6'octyl) aza-8 dioxa-5.11 pentadecane
- - N (hydroxy-8'dioxa-3,6 ' octyl) aza-8 tetraoxa-2,5,11,14 pentadecane
- - N (hydroxy-8'dioxa-3,6'octyl) aza-9 tetraoxa-3,6,12,15 heptadecane
- - N (hydroxy-8 'dioxa-3,6'octyl) aza-4,7,13,16-tetraoxa 10 nonadecane
- - N (hydroxy-8'dioxa-3,6'octyl) aza-11 tetraoxa-5,8,14,17 heneicosane
- - N (hydroxy-8'dioxa-3,6'octyl) aza-11 hexaoxa-2,5,8,14,17,20 heneicosane
- - N (hydroxy-8 'dioxa-3,6'octyl) aza-12 hexaoxa-tricosane 3,6,9,15,18,21
- - N (hydroxy-8'dioxa-3,6'octyl) aza-13 hexaoxa-4,7,10,16,19,22 pentacosane
- - N (hydroxy-8'dioxa-3,6'octyl) aza-14 hexaoxa-5,8,11,17,20,23 heptacosane
having the formula: - - N (hydroxy-11'trioxa-3 ', 6', 9'undecyl) aza-5 dioxa-2,8 nonane
- - N (hydroxy-11'trioxa-3 ', 6', 9'undecyl) aza-6 dioxa-3,9 undecane
- - N (hydroxy-11'trioxa-3 ', 6', 9'undecyl) aza-7 dioxa-4,10tridecane
- - N (hydroxy-11 ' trioxa-3', 6 ', 9'undecyl) aza-8 dioxa-5.11 pentadecane
- - N (hydroxy-11'trioxa-3 ', 6', 9'undecyl) aza-8 tetraoxa-2,5,11,14 pentadecane
- - N (hydroxy-11'trioxa-3 ', 6', 9'undecyl) aza-9 tetraoxa-3,6,12,15 heptadecane
- - N (hydroxy-11'trioxa-3 ', 6', 9'undecyl) aza-10 tetraoxa-4,7,13,16 nonadecane
- - N (hydroxy-11'trioxa-3 ', 6', 9'undecyl) aza-11 tetraoxa-5,8,14,17 heneicosane
- - N (hydroxy-11'trioxa-3 ', 6', 9'undecyl) aza-11 hexaoxa-2,5,8,14,17,20 heneicosane
- - N (hydroxy-11'trioxa-3 ', 6', 9'undecyl) aza-12 hexaoxa-3,6,9,15,18,21 tricosane
- - N (hydroxy-11'trioxa-3 ', 6', 9'undecyl) aza-13 hexaoxa-4,7,10,16,19,22 pentacosane
- - N (hydroxy-11'trioxa-3 ', 6', 9'undecyl) aza-14 hexaoxa-5,8,11,17,20,23 heptacosane
having the formula:
as well as polyoxaarylated amino alcohols having the formula:
Pour une bonne réalisation du procédé faisant l'objet de la présente invention, on pourra choisir des catalyseurs au nickel, du type nickel Raney ou Harshaw; la quantité de catalyseur pourra être comprise entre 1 et 15% du poids de bis(po- lyoxaalkyl)amine ou bis(polyoxaaryl)amine et de préférence entre 2 et 6%.For a good implementation of the process which is the subject of the present invention, it is possible to choose nickel catalysts, of the Raney or Harshaw nickel type; the amount of catalyst may be between 1 and 15% of the weight of bis (polyoxaalkyl) amine or bis (polyoxaaryl) amine and preferably between 2 and 6%.
Le rapport molaire polyalkylène glycol de formule (II)/bis (polyoxaalkyl)amine ou bis(polyoxaaryl)amine de formule (III) pourra également être compris entre 1, 5 et 10 fois la stoechiométrie et de préférence entre 2 et 6 fois la stoechiométrie.The polyalkylene glycol molar ratio of formula (II) / bis (polyoxaalkyl) amine or bis (polyoxaaryl) amine of formula (III) may also be between 1, 5 and 10 times the stoichiometry and preferably between 2 and 6 times the stoichiometry .
Le procédé faisant l'objet de l'invention pourra de préférence être réalisé en présence d'hydrogène, à une pression inférieure à 20 bars, et généralement à pression autogène, sous agitation violente jusqu'à disparition du polyalkylène glycol; cette opération dure de 2 à 10 heures et généralement de 3 à 4 heures. La quantité d'hydrogène pouvant être utilisée est de l'ordre de 1 à 10% du poids d'alkylène glycol mis en oeuvre et de préférence de l'ordre de 1 à 5%.The process which is the subject of the invention may preferably be carried out in the presence of hydrogen, at a pressure below 20 bars, and generally at autogenous pressure, with vigorous stirring until the polyalkylene glycol disappears; this operation lasts from 2 to 10 hours and general 3 to 4 hours. The amount of hydrogen that can be used is of the order of 1 to 10% of the weight of alkylene glycol used and preferably of the order of 1 to 5%.
L'eau formée au cours de la réaction pourra être éliminée du milieu réactionnel à l'aide d'un courant gazeux, tel que l'hydrogène quand celui- ci a été mis en œuvre ou de l'azote.The water formed during the reaction can be removed from the reaction medium using a gas stream, such as hydrogen when the latter has been used or nitrogen.
A titre d'exemples de polyalkylène glycol pouvant être mis en œuvre, on peut citer:
- - le diéthylène glycol
- - le triéthylène glycol
- - le tétraéthylène glycol.
- - diethylene glycol
- - triethylene glycol
- - tetraethylene glycol.
A titre d'exemples de bis(polyoxaalkyl)amines ou bis(polyoxaaryl)amines pouvant être mis en œuvre, on peut citer:
- - l'aza-5 dioxa-2,8 nonane
- - l'aza-6 dioxa-3,9 undecane
- - l'aza-7dioxa-4,10tridecane
- - l'aza-8 dioxa-5,11 pentadecane
- - 'aza-8 tetraoxa-2,5,11,14 pentadecane
- - l'aza-9 tetraoxa-3,6,12,15 heptadecane
- - l'aza-10 tetraoxa-4,7,13,16 nonadecane
- - l'aza-1 tetraoxa-5,8,14,17 heneicosane
- - l'aza-1 hexaoxa-2,5,8,14,17,20 heneicosane
- - l'aza-12 hexaoxa-3,6,9,15,18,21 tricosane
- - l'aza-13 hexaoxa-4,7,10,16,19,22 pentacosane
- - l'aza-14 hexaoxa-5,8,11,17,20,23 heptacosane
ayant pourformule:
ainsi que celles ayant pour formule:
- - aza-5 dioxa-2,8 nonane
- - aza-6 dioxa-3,9 undecane
- - aza-7dioxa-4,10tridecane
- - aza-8 dioxa-5.11 pentadecane
- - 'aza-8 tetraoxa-2,5,11,14 pentadecane
- - aza-9 tetraoxa-3,6,12,15 heptadecane
- - aza-10 tetraoxa-4,7,13,16 nonadecane
- - aza-1 tetraoxa-5,8,14,17 heneicosane
- - aza-1 hexaoxa-2,5,8,14,17,20 heneicosane
- - aza-12 hexaoxa-3,6,9,15,18,21 tricosan
- - aza-13 hexaoxa-4,7,10,16,19,22 pentacosane
- - aza-14 hexaoxa-5,8,11,17,20,23 heptacosane
having the formula:
as well as those having the formula:
Les aminoalcools polyoxaalkylés ou polyoxaarylés obtenus selon le procédé de l'invention peuvent être utilisés comme agents de complexation de cations. La présente invention a également pour objet cette application.The polyoxaalkylated or polyoxaarylated amino alcohols obtained according to the process of the invention can be used as cation complexing agents. The present invention also relates to this application.
Parmi les cations pouvant être complexés par lesdits aminoalcools polyoxaalkylés ou polyoxaarylés on peut citer: NH4 + et les cations dérivés des métaux des groupes IA à VIIA, VIII, IB à VB (Société Chimique de France) en particulier ceux dérivés des métaux alcalins ou alcalino-terreux tels que: Na, K, Li, Cs, Ca, Ba.Among the cations which may be complexed by said polyoxaalkylated or polyoxaarylated amino alcohols, mention may be made of: NH 4 + and the cations derived from the metals of groups IA to VII A , VIII, I B to V B (Société Chimique de France) in particular those derived from alkali or alkaline earth metals such as: Na, K, Li, Cs, Ca, Ba.
La complexation par les aminoalcools polyoxaalkylés ou polyoxaarylés de l'invention, de sels minéraux ou organiques des métaux ci-dessus cités ou de sels d'ammonium, permet de solubiliser lesdits sels ou d'améliorer la solubilité desdits sels dans des solvants organiques dans lesquels ils sont habituellement insolubles ou peu solubles.Complexation by the polyoxaalkylated or polyoxaarylated amino alcohols of the invention, of inorganic or organic salts of the metals mentioned above or of ammonium salts, makes it possible to dissolve said salts or to improve the solubility of said salts in organic solvents in which they are usually insoluble or poorly soluble.
Les exemples suivants sont donnés à titre indicatif et ne peuvent être considérés comme une limite du domaine et de l'esprit de l'invention.The following examples are given for information only and cannot be considered as limiting the scope and spirit of the invention.
Préparation du N(hydroxy 5' oxa 3' pentyl)aza 9 tétraoxa 3,6,12,15 heptadécane:
Dans un ballon tétracol de 2 litres, équipé d'une agitation, d'une arrivée d'hydrogène, d'une colonne et d'un condenseur pour recueillir l'eau, on charge:
On agite sous un courant d'hydrogène (11/mn) et on chauffe 3 heures à 170°C. On recueille 106 g d'eau et de produits légers correspondant à la déshydratation du diéthylène glycol. Après refroidissement, et séparation du Nickel Raney, le mélange est soumis à distillation pour récupérer 888g de diéthylène glycol et 280 du produit cherché qui bout à Eb1:193°.Stirred under a stream of hydrogen (11 / min) and heated for 3 hours at 170 ° C. 106 g of water and light products are collected, corresponding to the dehydration of diethylene glycol. After cooling, and separation of the Nickel Raney, the mixture is subjected to distillation to recover 888 g of diethylene glycol and 280 of the sought product which boils at Eb 1 : 193 °.
Le rendement atteint 55% sur l'amine secondaire engagée.The yield reaches 55% on the secondary amine used.
Préparation du N(hydroxy-8' dioxa 3',6' octyl)aza 9 tétraoxa 3,6,12,15 heptadécane:
Dans le même appareillage que l'exemple 1, et dans les mêmes conditions de travail, on fait réagir:
Après 3 heures de chauffage à 180°C, puis filtration du Nickel Raney, le mélange est soumis à distillation pour éliminer le triéthylène glycol. On récupère 610 du produit attendu sous forme d'un liquide brun foncé présentant une pureté de 88,1%.After 3 hours of heating to 180 ° C., then filtration of the Nickel Raney, the mixture is subjected to distillation to remove the triethylene glycol. 610 of the expected product are recovered in the form of a dark brown liquid having a purity of 88.1%.
Le rendement sur l'amine secondaire chargée atteint 71 %.The yield on the charged secondary amine reaches 71%.
Préparation du N(hydroxy 8' dioxa 3',6' octyl) aza 11 hexaoxa 2,5,8,14,17,20 heneicosane.
Dans les mêmes conditions qu'à l'exemple 1, on fait réagir:
- - aza 11 hexaoxa 2,5,8,14,17,20 heneicosane
250 g (0,80 mole) - - triéthylène glycol 550 g (3,66 moles)
- - NickeyRaney déshydraté 50 g
- - aza 11 hexaoxa 2,5,8,14,17,20 heneicosane
250 g (0.80 mole) - - triethylene glycol 550 g (3.66 moles)
- - NickeyRaney dehydrated 50 g
Après 5 heures de réaction à 180° sous courant d'hydrogène, le Nickel Raney est filtré et le filtrat est étété jusqu'à 300° sous 0,1 mmHg (13,3 Pa). On obtient 325 g de l'aminoalcool cherché, soit un rendement de 92,2%.After 5 hours of reaction at 180 ° under a stream of hydrogen, the Nickel Raney is filtered and the filtrate is summer up to 300 ° under 0.1 mmHg (13.3 Pa). 325 g of the desired amino alcohol are obtained, ie a yield of 92.2%.
Préparation du N(hydroxy-5' oxa-3' pentyl)aza-8 tetraoxa-3,6,11,14 pentadécane.
Dans les mêmes conditions qu'à l'exemple 1, on fait réagir:
- - aza-8tétraoxa-3,6,11,14pentadécane
676,5 g (3 moles) - - diéthylèneglycol 1285 g (12 moles)
- - nickel Raney déshydraté 218 g
- - aza-8tetraoxa-3,6,11,14pentadecane
676.5 g (3 moles) - - diethylene glycol 1285 g (12 moles)
- - dehydrated Raney nickel 218 g
On maintient 3 heures à 180-185°C sous un courant de 2g/h d'hydrogène.Maintained for 3 hours at 180-185 ° C under a stream of 2 g / h of hydrogen.
Après séparation du nickel Raney, la masse est distillée pour récupérer l'excès de diéthylèneglycol et 662 de l'aminoalcool attendu qui bout à Eb1 = 200°C.After separation of the Raney nickel, the mass is distilled to recover the excess of diethylene glycol and 662 of the expected amino alcohol which boils at Eb 1 = 200 ° C.
Le rendement par rapport à l'amine secondaire engagée est de 71,5%.The yield relative to the secondary amine used is 71.5%.
Préparation du N(hydroxy-8' dioxa-3',6' oc- tvl)aza-8 tétraoxa-2.5.11.14 pentadécane.
Dans les mêmes conditions qu'à l'exemple 1, on fait réagir:
Après 3 heures de chauffage à 180°C, filtration du nickel Raney et distillation pour éliminer le triéthylène glycol, on récupère 508 de l'aminoalcool attendu qui bout à Eb0,3 = 193°C.After 3 hours of heating to 180 ° C., filtration of the Raney nickel and distillation to remove the triethylene glycol, 508 of the expected amino alcohol are recovered which boils at Eb 0.3 = 193 ° C.
Le rendement par rapport à l'amine secondaire est de 72%.The yield relative to the secondary amine is 72%.
Propriété complexante du N(hydroxy 8' dioxa 3',6' octyl)aza II hexaoxa 2,5,8,14,17,20 heneicosane.Complexing property of N (hydroxy 8 'dioxa 3', 6 'octyl) aza II hexaoxa 2,5,8,14,17,20 heneicosane.
Solùbilisation des thiocyanates alcalins dans le chlorure de méthylène.Solubilization of alkali thiocyanates in methylene chloride.
Ce test mettant en évidence la propriété complexante du produit préparé à l'exemple 3 est réalisé comme suit:
- Dans un erlenmeyer de 50 ml équipé d'un réfrigérant ascendant et d'un agitateur magnétique, on introduit 10 ml de chlorure de méthylène anhydre et purifié (c'est-à-dire exempt de stabilisant).
- 10 ml of anhydrous and purified methylene chloride (that is to say free from stabilizer) are introduced into a 50 ml Erlenmeyer flask equipped with an ascending cooler and a magnetic stirrer.
On ajoute ensuite:
- - 0,001 mole d'un thiocyanate alcalin choisi parmi les thiocyanates de Li, Na et K;
- - 0,001 mole d'agent complexant à tester.
- - 0.001 mole of an alkali thiocyanate chosen from thiocyanates of Li, Na and K;
- - 0.001 mole of complexing agent to be tested.
Après avoir agité le mélange pendant 10 mm à la température ambiante, on centrifuge; la solution claire ainsi obtenue est analysée par spectrométrie de flamme.After the mixture has been stirred for 10 mm at room temperature, it is centrifuged; the clear solution thus obtained is analyzed by flame spectrometry.
Le test est également réalisé en l'absence d'agent complexant à tester.The test is also carried out in the absence of complexing agent to be tested.
Les résultats obtenus sont les suivants:
- - Solubilisation de Li S C N
- - solubilité mesurée: 690 mg/I
- - solubilité maximum calculée: 690 mg/I
- - taux de solubilisation: 100%
- - complexes formé:
- - Solubilité mesurée sans agent complexant: <1 mg/1
- - Solubilisation de NaSCN
- - Solubilité mesurée: 2300 mg/l
- - solubilité maximum calculée: 2300 mg/l
- - taux de solubilisation: 100%
- - complexe formé:
- - Solubilité mesurée sans agent complexant: <1 mg/I
- - Solubilisation de KSCN
- - solubilité mesurée: 3380 mg/I
- - solubilité maximum calculée: 3910 mg/l
- - taux de solubilisation: 86,4%
- - complexe formé:
- - Solubilization of Li SCN
- - measured solubility: 690 mg / I
- - maximum calculated solubility: 690 mg / I
- - solubilization rate: 100%
- - complexes formed:
- - Solubility measured without complexing agent: <1 mg / 1
- - Solubilization of NaSCN
- - Measured solubility: 2300 mg / l
- - maximum calculated solubility: 2300 mg / l
- - solubilization rate: 100%
- - complex formed:
- - Solubility measured without complexing agent: <1 mg / I
- - Solubilization of KSCN
- - measured solubility: 3380 mg / I
- - maximum calculated solubility: 3910 mg / l
- - solubilization rate: 86.4%
- - complex formed:
Les résultats ci-dessus peuvent être résumés dans le tableau suivant:
Propriété complexante du N(hydroxy-5' oxa-3' pentyl) aza-8 tétraoxa-3,6,11,14 pentadécane Solubilisation des thiocyantes alcalins dans le chlorure de méthylène.Complexing property of N (5-hydroxy-oxa-3 'pentyl) aza-8 tetraoxa-3,6,11,14 pentadecane Solubilization of alkaline thiocyants in methylene chloride.
Le test décrit à l'exemple 6 est réalisé en mettant en oeuvre comme agent complexant à tester le produit de l'exemple 4.The test described in Example 6 is carried out using as a complexing agent to test the product of Example 4.
Les résultats sont les suivants:
- - taux de solubilisation de LiSCN: 97% NaSCN: 98% KSCN: 93%
- - complexes formés:
- - LiSCN solubilization rate: 97% NaSCN: 98% KSCN: 93%
- - complexes formed:
Propriété complexante du N(hydroxy-8' dioxa-3',6' octyl/aza-8 tétraoxa-2,5,11,14 pentadécaneComplexing property of N (8-hydroxy-dioxa-3 ', 6' octyl / aza-8 tetraoxa-2,5,11,14 pentadecane
Solubilisation des thiocyanates alcalins dans le chlorure de méthylène.Solubilization of alkali thiocyanates in methylene chloride.
Le test décrit à l'exemple 6 est réalisé en mettant en œuvre comme agent complexant à tester le produit de l'exemple 5. Les résultats sont les suivants:
- - taux de solubilisation de LiSCN: 99% NaSCN: 100% KSCN: 93%
- - complexes formés:
- - solubilization rate of LiSCN: 99% NaSCN: 100% KSCN: 93%
- - complexes formed:
Claims (14)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT81401325T ATE5398T1 (en) | 1980-08-27 | 1981-08-20 | PROCESSES FOR THE PREPARATION OF POLYOXALKYLATED OR POLYOXAARYLATED AMINOALCOHOLS AND THEIR USE AS CATION COMPLEXING AGENTS. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR8018561A FR2489315A1 (en) | 1980-08-27 | 1980-08-27 | NOVEL POLYOXAALKYL AMINOALCOHOLS, PROCESS FOR THEIR PREPARATION AND THEIR APPLICATION AS CATION COMPLEXATION AGENTS |
FR8018561 | 1980-08-27 |
Publications (2)
Publication Number | Publication Date |
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EP0047206A1 EP0047206A1 (en) | 1982-03-10 |
EP0047206B1 true EP0047206B1 (en) | 1983-11-23 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP81401325A Expired EP0047206B1 (en) | 1980-08-27 | 1981-08-20 | Process for preparation of aminoalcohols polyoxa-alkylated or polyoxa-arylated and their use as cation complexing agents |
Country Status (7)
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US (2) | US4429160A (en) |
EP (1) | EP0047206B1 (en) |
JP (1) | JPS5772942A (en) |
AT (1) | ATE5398T1 (en) |
BR (1) | BR8105459A (en) |
DE (1) | DE3161506D1 (en) |
FR (1) | FR2489315A1 (en) |
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DE3826608A1 (en) * | 1988-08-05 | 1990-02-08 | Basf Ag | FUELS CONTAINING POLYETHERAMINE OR POLYETHERAMINE DERIVATIVES FOR OTTO ENGINES |
US7247606B2 (en) * | 2001-11-05 | 2007-07-24 | Cognis Corporation | Branched reaction products |
WO2006017432A2 (en) * | 2004-08-02 | 2006-02-16 | New York University | A polynucleotide nanomechanical device that acts as an artificial ribosome and translates dna signals into polymer assembly instructions |
CN104109235B (en) * | 2014-05-30 | 2017-07-18 | 厦门赛诺邦格生物科技股份有限公司 | A kind of single functionalized poly (ethylene glycol), preparation method and its bio-related substance with nitrogen-atoms branch centers |
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US2529923A (en) * | 1943-04-22 | 1950-11-14 | Eastman Kodak Co | 2-(2-hydroxyethoxy) ethylamine |
US2928877A (en) * | 1957-05-10 | 1960-03-15 | Wyandotte Chemicals Corp | Process for preparing oxyalkyleneamines |
GB897163A (en) * | 1959-07-02 | 1962-05-23 | Ciba Ltd | New aminoalcohols and process for their manufacture |
US3356727A (en) | 1963-06-25 | 1967-12-05 | Marchon Products Ltd | Alkyl-and alkaryl-oxyalkyl-nu-hydroxyalkyl amine oxides |
US3352916A (en) * | 1964-04-15 | 1967-11-14 | Atlas Chem Ind | Aminated polyoxyalkylene fatty amines |
US3456012A (en) | 1965-10-22 | 1969-07-15 | Cargill Inc | Polyoxyolefin adducts of gamma-alkoxypropylamines |
US4009255A (en) | 1966-07-26 | 1977-02-22 | Societe Anonyme Dite: L'oreal | Hair treating compositions containing cationic surface active agents |
US3714259A (en) * | 1970-08-20 | 1973-01-30 | Jefferson Chem Co Inc | Production of linear polyethylene polyamines |
US3847992A (en) * | 1973-03-12 | 1974-11-12 | Jefferson Chem Co Inc | Partially aminated polyoxyalkylene polyols |
US3957875A (en) * | 1974-06-10 | 1976-05-18 | Union Carbide Corporation | Synthesis of bis[2-(N,N-dimethylamino)ethyl] ether |
US4151204A (en) * | 1975-06-27 | 1979-04-24 | Teijin Limited | Process for preparing amino alcohols |
GB1588079A (en) * | 1977-09-12 | 1981-04-15 | Texaco Development Corp | Surface-active oxyalkylated amines |
FR2423478A1 (en) * | 1978-04-21 | 1979-11-16 | Rhone Poulenc Ind | NEW PROCESS FOR PREPARING TRIS (POLYOXAALKYL) AMINES |
DK394779A (en) | 1978-10-12 | 1980-04-13 | Henkel & Cie Gmbh | QUARTERNY AMMONIUM COMPOUNDS A PROCEDURE FOR PREPARING ILLING THEREOF AND THEIR USE AS A TEXTILE ANTIQUITIES |
FR2450120A1 (en) * | 1979-03-02 | 1980-09-26 | Rhone Poulenc Ind | PROCESS FOR SOLUBILIZING ORGANIC OR MINERAL SALTS IN ORGANIC SOLVENTS |
-
1980
- 1980-08-27 FR FR8018561A patent/FR2489315A1/en active Granted
-
1981
- 1981-08-20 EP EP81401325A patent/EP0047206B1/en not_active Expired
- 1981-08-20 AT AT81401325T patent/ATE5398T1/en active
- 1981-08-20 DE DE8181401325T patent/DE3161506D1/en not_active Expired
- 1981-08-21 JP JP56130409A patent/JPS5772942A/en active Granted
- 1981-08-25 US US06/296,214 patent/US4429160A/en not_active Expired - Fee Related
- 1981-08-26 BR BR8105459A patent/BR8105459A/en unknown
-
1983
- 1983-01-05 US US06/455,898 patent/US4504682A/en not_active Expired - Fee Related
Also Published As
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DE3161506D1 (en) | 1983-12-29 |
JPS5772942A (en) | 1982-05-07 |
US4429160A (en) | 1984-01-31 |
EP0047206A1 (en) | 1982-03-10 |
US4504682A (en) | 1985-03-12 |
BR8105459A (en) | 1982-05-11 |
JPS6230982B2 (en) | 1987-07-06 |
FR2489315A1 (en) | 1982-03-05 |
FR2489315B1 (en) | 1983-11-25 |
ATE5398T1 (en) | 1983-12-15 |
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